Storage battery material



April 25, 1961 E. J. DUNN, JR, ETAL STORAGE BATTERY MATERIAL Filed June 10, 1959 Fig. I.

INVENTORS tates i ate 2,981,776 Bat-exited Apr. 25, 1961 STORAGE BATTERY MATERIAL Edward Joseph Dunn, Jr., Port Washington, N.Y., and Joseph Anthony Orsino, Mountain Lakes, N.J., .as- 'signors to National LeadCompany, New York, N;Y., a corporation of New Jersey ,Filed June -10,'1959,,Ser. No.-;819,444 6.Claims. (Cl.'136-'-27) This invention relates to a material foruse in the manufacture of lead-acid storage batteries and has particular vreferenceto a composition of matter comprising lead oxide, finely'divided metallic lead and lead sulfate of various degrees of basicity.

This is a continuation-in-partof our copendingapplication Serial No. 541,540, filed,October 19, 1955, now abandoned.

Ordinarily, storage battery-plates are made from a hardened lead alloy grid or framework, into which .is

pressed'a paste made with lead oxide, water and diluted I lead-sulfate,,l4% water, and the balance lead oxide and fgenerallyhasa density of approximately 4.4 grams per cubic centimeter. The function of water in the paste is to produce a plastic state and to coalesce the individual :ture with water alone. in the mixing machinery. -Unfortunately, however, such efforts have not been too'successful since they necessitate the preparation of lead sulfate in the .dry state, in itself a costly procedure, and such lead sulfate does not always possess the proper crystal structure and size compatible with satisfactory plate and battery capacity and life.

' It is therefore an object of this invention to provide an improved method for the production ofcompositions suitable for use as storage battery active materials. .A further object is to provide an improved method for productionof-lead oxide-lead sulfate compositions suitable for use as storage battery active materials. Another object'is to provide such a method, which avoidsaddition of sulfuric acid to aqueous lead oxide pastes. Still another object is to provide such a method, which eliminates the necessity of separately preparing lead sulfate. Other objects and advantages will become-apparent from the following more complete description and claims.

"Broadly, this invention contemplates a method of preparing a composition suitable for use as active material in lead-acid storage battery plates which comprises the sulfuric acid. Such paste generally contains about 15% steps of reacting metallic lead at elevated temperatures simultaneously with air and with sulfuric acid.

Preferably, the process of this invention is carried out in a continuousfurnace designed to oxidize metallic lead Qto lead oxide, such as, for example, the type of continuous particles so that the lead oxide may be compressed into the grid. If water alone is mixed with the oxide, however,

the -maximum amount of water which will still retain plastic properties in the paste will result in a paste density of around'5.3 grams per cubic centimeter. If plates are prepared from such a paste, the resultant dried plate will be'impervious to the battery electrolyte and produce plates 1 which are of low capacity and which will distort on discharge and eventually short circuit the battery.

I In order to increase the porosity of the plate and to eliminate distortion during discharge, it has been customary to include a certain quantity of lead sulfate in the paste and'the lead sulfate is generally produced by the addition of dilutesulfuric acid in aqueous solution to the oxide-water paste. Since the specific gravity of lead sul- 'fate is"6';3 as compared to '9,3 for lead oxide, the presence oflead'sulfate in moderate amount, say from 6 to calculatedas normallead sulfate, in the pasteresults in a bulking action which increases the porosityof the paste. The additionfof sulfuric acid; to the lead oxide paste -mix, however, has certain disadvantages. -When sulfuric .acid is added to aalead oxide andwaterpaste to produce 7 1 ;lead sulfate, an exothermic reactionresults with the eVo-' lution of considerable heat. This heat must be dis sipated and'exp'ensive water jackets or blower fansv must be. in-

stalled in the mixing equipment. Further, the heat generated causes the evaporation of largequantities of water in the form of steam resulting in variationsin the amount of water retained bythe mix and variations in density of the mixture. I Still-further,the-temperature of the mixture is raised to a point where undesirable side reactions and presetting may takeplace making thepaste difiicult to handle in mechanical pasting machines and resulting in decreased capacity and life in the battery. I

gStill further, the blending,- testing, and addition of acid to the mixing machines are time consuming, expensive and 0f a" corrosive nature. The sulfuric acid corrodes'the v j L- ous metal portions'of the mixing and handling equipment.

- Attempts have-beenmade in the past, directed-towards obviating these disadvantages by=preblending' lead sulfate 7 iyitht he oxide in the dry state and then preparing the mix- .furnace' knownas the Barton pot.

Preferably, also, theprocess is carried out in such'a manner that free metallic lead is always present, resulting in a'composition which comprises some metallic lead along with lead oxide and lead sulfate. V e

The temperature employed in the .reactionchamber should be at least about 621 F., assuring thereby that thelead does not solidifyin the chamber, and may be as high as desiredshort of the melting point of lead oxide,

about '1 6-30? F. .In practice, it'has been found most convenient to maintain .aftemperature in the reaction zone" between 650 and 1000 F.

It has been determined that after the pot has been initially started no extraneous heat is required to maintain these temperatures since the exothermic chemical action of the lead oxidation supplies all of the requisite h ta i .The'manner in which the sulfuric acidis added tothe furnace (oxide pot) is not limited except that the acid and air, which will normally bepadded in the form of a stream to the furnace particularly where the reaction is carried out in a continuous fashion, are present -simultaneously. As will be more fully brought out inthe description of the accompanying drawing the acidm'aybe added in various ways.

or concentrated, directlyto thejair stream 'as-o'rbefore the latter enters "the furnace This. particular manner J of addition. appears to provide a more uniform dispersion of the acid in the reaction mixture, resulting in a more homogeneous product. v

The employment of H 80 in the practice of this invention, is critical in that it cannot be replaced by S0 7 It has been established that if S0 is substituted for H 50 little or no lead sulfate'is formed. Also, iniusing H 30 little or no S03or S0 is produced in the atmosphere of the'furnace since the reaction between the acid'and litharge is practically "instantaneous. Free H 80 cannot existin the presence of a relativelylarge amount of lit-h I arge. Therefore; beforeftheH SO can even beheated to any great extent and subsequently be reduced,it re'acts to form the sulfate. :This'h'asf been born out by quantitative studies, determinations and by the fact-..that practically no'corrosionfof thei'r'on machinery (stirrer; b'affles, hoppers, etc.) {takes place would bethe case It has been found preferable however;toadd the sulfuric acid, which maybe diluted were H 80 to remain or SO; phere'ofthe furnace. l v 1 Infthe practice of this invention it is generally desirable to produce a productco'iisis'ting ofabout ltto'5 0% l'b, to 70% PbO and6to PbSO41" f The presence of free lead inthe lead oxidedead sulfate I her 9 be produced in the atrnos 1 1 composition imparts desirablepropertiesto the subsea quently prepared" storage battery paste," For example,'

afte'r' the freshly prepared moistened paste has been ap-' plied to a battery grid, the paste undergoes a drying op:-

oration. This results in thepaste contracting within the grid framework, thereby loosening the astc-tO grid bond acts this shrinking of the dryingpaste and assures a strong I and causes dried paste particles'to falli err the'plates. The free 3 lead; within the paste composition, by chemically,

' 'convertingtolead oxide and thereby expanding, counter? paste-to grid bond." This lead oxidizing reaction, being Pastes containing freelead; under about 10%v as a component of sufficiently exothermic, also helps to carry thedrying op oration to completion: The amount of free lead present ina paste must however-'be controlled. Pastes containing too high,.over'50% Pb: will eventually produce, blistering 7 and/or spalding of the spongelead in the pasted negative i plates.

will notetiectively produce the desired hydroscttiug properties alluded to, above. In the, practice ofthis, invention the metallic lead con- 1 Z tent isgenerally controlled by regulating the rate of metal v v Ifeedand the operating temperatures; high temperatures 1 i producingfproducts of low metal contents, low temperal itures producing Iproductsof high metal contents. :In ad- 3 dition, it will be understood that since the process of this C 3 avenues is continuous the products are continuously b g %i 9 was 9 u withdrawn at a stage where some materials have under- 1 a 2 gone a'cornpiete reaction and others have not. Forin: stance, unoxidized leadis i withdrawn the products of this invention. a 1 I I In regard to the litharge percentages, a litharge content a p under aboutlO% is apt to hinder {the formation of%PbSO i l Althoughno'adverse efiect, per, se; results inihaving the l 'lith'arge content exceedabout 70%., it is limited however,

' due to the/Pb and PbSQ; amounts desired in' the end prod- Y In another similar systemgernployiug a pot equipped v with aninl e't funnelf9 during which: the metal feed :1 i was 200 lbs. per hour; s1.lfuric'acid, 81;6% S0 :ad I through funnel 9 by means ofv a :convenh'onal pipette, feed rate vvas li gal; perhour and the gobserved ternperatur'e was'7'UQ" F., a product consistingfof'about 5? l The lead-lead isult'ate-litharge mixturesiprepared by the above exampleswere used :to make storage battery; plates not. For purposes of simplicity the above recited litharge percentages and thoserecited'in the following examples represent free litharge and the chemically combined'litlv arge present due tothe formation of lead sulfates.

In the accompanying drawing Figure 1 represents an elevation of afurnace designed for carrying into effect the, a

present invention. Figure 2.iepresents a furnace, also designed for carrying into effect the present invention, and is meant to represent a furnace identical, in all respects, to the furnace represented by Figure 1 except for the additionof a funnel which is indicated by reference num- The 'pot l, appropriately mounted so as to be capable of being initially heated, has a fstirrer 2 driven at about 150 rpm. constant speedby a motor drive not shown, a

fixed baffle or dash plate 3, an air and sulfuric acid inlet 760 FL, a product consisting of about and 6%PbSO was while theprocesswas in operation. Lead was then Sim- :ilarly' fed in the pot 1 at: arateof 100 lbs. per hour. Simuttancously, air Wasdrawn' in through inlet 4 by "means of a suction fan, not shown, located above the I settling chamber, Sulfuricacid, 81.6%, S0 wasthen added at a rate, of /2 gal. per-hour by means of a stand-v I arcl automatic'pipette, not showmto theair stream asit passed through inlet Theresulting mixture of Pb,

PhD and PbSQ by meansof the air stream, was then f :drawn' out of the, potthrou'gh uptake into the settling chamber, not shown. The operating temperature was observed, by means of pyrometer 6, tobe aboutBOO F. v Periodic analysis of the continuous v 7 product. consisting I of about l2% Pb, 68% PhD and I '20%PbSO FEW"??? H if. I

r 'asi'milarsystem, during which the metal feed rate 0 was'2OO Ibsperhouusulfuricacid, 44. 9% S0 feed rate ,Wa's /Zi gal; per hourzand; the recorded, temperaturewas produced. 't'axtirfhpl III Example IV 1 accordingltofthe"followinggeneral procedure.

Positivepa'stes were; prepare-d b3 adding. water to the tures vandthen;mixing for liminutes ina conventional 1 t battery pa ts mi e 1 Negative. pastes were prepared adding first lamp ,black, blanc fixe, and an organic material to the mixture and then adding water to, the expander mixtures.

4,. an uptake 5 leading to a settling chamber not shown, a

pyrometer 6, a trough 7 through which molten lead is fed into the pot and a guard plate 8 which minimizes an splashing. y 1 As an alternative method for adding the sulfuric acid, it

may be added, instead of through the air'intake 4, in a furnace so equipped, through affunnel 9 (Figural) by Jmeans of a conventional automatic pipette not shown.

By way of illustration, thefollowing examples are offered as illustrative embodiments of the-invention with regard to the preparationof the desired material of this Iinvention in a furnace commonly-referred to as; the

Barton-pot. i a if 1 qExample l leadiwasfed intolthe" potg through troughtomore or The following table shows the amounts of water added to each of the mixtures and the resulting paste densities.

' TABLE 1 v a H 7 Added water-ice. Paste Density, Pb-PbSO4'-Pb0 Mixtures per pound ot'mixture grams per 0. cm.

made by methods l t of examples. t y i positive Negative positive negative paste paste paste paste Example L- "75 4.4 4. Example II. 70 4. 4 4. Example Ill 86 3.9 4.

The resulting pastes weresubsequently applied to batl l teryfplates; andlwere suitable for use in heavy duty type A fter-the pot 1, was properlyheated;ennugh molten b'attierpias i? h fl t ng life pasted plates are qu red i it i l The process of this invention provides an improved method for thegproductionof compositions suitable for use in storagebattery active material pastes. It is simple ,andl'easily, carried 1 out as compared with the processes heretofore available-for producing compositions ,of the type desired, and is largely frceffromlztheicorrosion difficulties experienced; with;the,prior-processes. The compositions produccd, oreoverypossess improved proper- .ties, particul tion.

arly withresp'ect to uniformity er composi- 3 Wlnlegthe ,forcgoinguex'amples illustrate certain preferred procedures;andiproportions,'noun due limitations should be vdeduced;.therfromg.and the.Iinvention is not to be limited, except as set forth in the appended claims.

process showed a ate :led

We claim:

1. A method of preparing a composition suitable for use as active material in lead-acid storage battery plates wich comprises the steps of continuously reacting metallic lead at a temperature between 621 F. and 1630 F. simultaneously with air and with sulfuric acid, said sulfuric acid reacting substantially instantaneously to form lead sulfate prior to any substantial thermal decomposition of said acid, and continuously withdrawing a product comprising lead oxide in amount between and 70 percent, lead sulfate in amount between 6 and 35 percent and metallic lead in amount between 10 and 50 percent.

2. A method of preparing a composition suitable for use as active material in lead-acid storage battery plates which comprises the steps of continuously reacting metallic lead at a temperature between 621 F. and 1630" F. simultaneously with air and with sulfuric acid, said reaction being carried out in the presence of free metallic lead, said sulfuric acid reacting substantially instantaneously to form lead sulfate prior to any substantial thermal decomposition of said acid, and continuously withdrawing a product comprising lead oxide in amount between 10 and 70 percent, lead sulfate in amount between 6 and 35 percent and metallic lead in amount between 10 and 50 percent.

3. A method of preparing a composition suitable for use as active material in lead-acid storage battery plates which comprises the steps of continuously reacting metallic lead at a temperature between 650 and 1000 F. simultaneously with air and with sulfuric acid, said sulfuric acid reacting substantially instantaneously to form lead sulfate prior to any substantial thermal decomposition of said acid, and continuously withdrawing a product comprising lead oxide in amount between 10 and 70 percent, lead sulfate in amount between 6 and 35 percent and metallic lead in amount between 10 and 50 percent.

4. A method of preparing a composition suitable for use as active material in lead-acid storage battery plates which comprises the steps of continuously reacting metallic lead at a temperature between 621 F. and 1630 F. with air in a reaction zone, said air being fed in the form of a stream to said reaction zone, and concurrently adding sulfuric acid to said stream of air said sulfuric acid reacting substantially instantaneously to form lead sulfate prior to any substantial thermal decomposition of said acid, and continuously withdrawing a product comprising lead oxide in amount between 10 and 70 percent, lead sulfate in amount between 6 and 35 percent vand metallic lead in amount between 10 and percent.

5. A method of preparing a composition suitable for use as active material in lead-acid storage battery plates which comprises the steps of continuously reacting metallic lead at a temperature between 621 F. and 1630" F. with air in a recation zone, said air being admitted in the form of a stream to said reaction zone, maintaining free metallic lead in said reaction zone, and continuously adding sulfuric acid to said reaction zone, said sulfuric acid reacting substantially instantaneously to form lead sulfate prior to any substantial thermal decomposition of said acid, and continuously withdrawing a product comprising lead oxide in amount between 10 and percent, lead sulfate in amount between 6 and 35 percent and metallic lead in amount between 10 and 50 percent.

6. A method of preparing a composition suitable for use as active material in lead-acid storage battery plates which comprises the steps of continuously reacting metallic lead at a temperature between 621 F. and 1630 F. with air in a reaction zone, said air being fed in the form of a stream to said reaction zone, and concurrently adding sulfuric acid to said stream of air, said sulfuric acid being added dropwise to said stream of air, said sulfuric acid reacting substantially instantaneously to form lead sulfate prior to any substantial thermal decomposition of sad acid, and continuously withdrawing a product comprising lead oxide in amount between 10 and 70 percent, lead sulfate in amount between 6 and 35 percent and metallic lead in amount between 10 and 50 percent.

References Cited in the file of this patent UNITED STATES PATENTS 1,187,949 White June 20, 1916 1,524,315 Schaeffer et al Ian. 27, 1925 2,182,479 Johnstone Dec. 5, 1939 2,235,487 Mayer Mar. 18, 1941 2,300,627 Merson Nov. 3, 1942 

6. A METHOD OF PREPARING A COMPOSITION SUITABLE FOR USE AS ACTIVE MATERIAL IN LEAD-ACID STORAGE BATTERY PLATES WHICH COMPRISES THE STEPS OF CONTINUOUSLY REACTING METALLIC LEAD AT A TEMPERATURE BETWEEN 621*F. AND 1630*F. WITH AIR IN A REACTION ZONE, SAID AIR BEING FED IN THE FORM OF A STREAM TO SAID REACTION ZONE, AND CONCURRENTLY ADDING SULFURIC ACID TO SAID STREAM OF AIR, SAID SULFURIC ACID BEING ADDED DROPWISE TO SAID STREAM OF AIR, SAID SULFURIC ACID REACTING SUBSTANTIALLY INSTANTANEOUSLY TO FORM LEAD SULFATE PRIOR TO ANY SUBSTANTIAL THERMAL DECOMPOSITION OF SAID ACID, AND CONTINUOUSLY WITHDRAWING A PRODUCT COMPRISING LEAD OXIDE IN AMOUNT BETWEEN 10 AND 70 PERCENT, LEAD SULFATE IN AMOUNT BETWEEN 6 AND 35 PERCENT AND METALLIC LEAD IN AMOUNT BETWEEN 10 AND 50 PERCENT. 